CN102754249A - Non-aqueous cell having a mixture of fluorinated carbon cathode materials - Google Patents

Non-aqueous cell having a mixture of fluorinated carbon cathode materials Download PDF

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CN102754249A
CN102754249A CN2010800630152A CN201080063015A CN102754249A CN 102754249 A CN102754249 A CN 102754249A CN 2010800630152 A CN2010800630152 A CN 2010800630152A CN 201080063015 A CN201080063015 A CN 201080063015A CN 102754249 A CN102754249 A CN 102754249A
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cathode material
fluorocarbons
electrochemical cells
aqueous electrochemical
arbitrary
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CN102754249B (en
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D.张
M.德斯蒂芬
V.武
J.C-H.常
H.J.邦
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EaglePicher Technologies LLC
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EaglePicher Technologies LLC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The present disclosure relates generally to a cathode material suitable for use in a non-aqueous electrochemical cell that comprises a mixture of fluorinated carbon materials, and more particularly such a cell that comprises a mixture of three fluorinated carbon materials that each have distinct (from each other) discharge profiles (e.g., distinct voltages and capacities). The present disclosure additionally relates to a non-aqueous electrochemical cell comprising such cathode material and, in particular, to such a non-aqueous electrochemical cell that is lithium-based (i.e., a lithium, or lithium ion, non-aqueous electrochemical cell).

Description

Non-aqueous electrolyte battery with mixture of fluorocarbons cathode material
The cross reference of related application
The application requires the rights and interests of the U.S. Provisional Application No. 61/266,628 of submission on December 4th, 2009, and this provisional application integral body is by reference incorporated among the application.
Invention field
The present invention relate generally to be suitable for non-aqueous electrochemical cells ( Non-aqueous electrochemical cell) cathode material; The mixture of said power brick fluorinated material with carbon element, and the present invention more specifically relates to such battery, and it comprises the mixture of three kinds of fluorinated carbon materials; Every kind of said fluorinated carbon material has different (each other) discharge curve (for example, different voltages with different and capacity).In addition, the present invention relates to comprise the non-aqueous electrochemical cells of such cathode material, and relate in particular to such non-aqueous electrochemical cells into lithium base (that is the non-aqueous electrochemical cells of lithium or lithium ion).
Background of invention
Lithium electrochemical cells (more generally be called battery pack ( Batteries)) be widely used in various military and the consumer products.A lot of these product utilization high-energy and high-power battery group.Part is owing to the miniaturization of portable electric appts, and people hope to develop power capacity and be improved useful life even more small-sized lithium battery.A kind of method of the more compact battery that improves in order to the developed horse power capacity is to develop more high-octane cathode material.
An instance of high-energy cathode material is fluorocarbons (being CF).Up to now; Li anode/CF cathode cell has been used for the equipment of low-power or mid power; Said equipment for example comprises that (discharge rate for example extends to about 2 * 10 from about 0.1W/cc (that is about C/10) usually for military affairs, Aero-Space, electronics and medical field -5W/cc (that is, about C/50,000)).In said medical field, Li anode/CF cathode cell is used for the Medical Devices of the implantable energy of requirement low-power or mid power at present.Yet; Although said battery has high-energy-density and good stable property; But because the high resistivity of cathode substrate causes the power capacity of low-work voltage and qualification, said Li/CF cathode cell is not used for rate applications (like implantable cardiac defibrillator (or ICD)) as yet.
Therefore, exist to the demand of the cathode material that is suitable for high voltage applications (comprise two-forty pulsed discharge use), and especially have the demand that supplementary features is the cathode material that high-energy-density is such.
Summary of the invention
In brief, therefore the present invention relates to non-aqueous electrochemical cells, comprising: (i) anode; (ii) mixed cathode; It comprises that the first fluorocarbons cathode material, the second fluorocarbons cathode material and the 3rd fluoridize carbon cathode material; Wherein, (a) the said first or the 3rd fluoridizes carbon cathode material and has and the different average degree of fluorination of the said second fluorocarbons cathode material, and (b) the said first fluorocarbons cathode material derives from petroleum coke, and the said the 3rd fluoridizes carbon cathode material and derive from petroleum asphalt; (iii) be arranged on the dividing plate between said anode and the said negative electrode; And the nonaqueous electrolytic solution that (iv) is communicated with said anode, said negative electrode and said dividing plate fluid.Randomly, the said second fluorocarbons cathode material derives from petroleum coke equally, and/or the said first and the 3rd fluoridizes carbon cathode material and have roughly the same average degree of fluorination.
Additionally or alternatively, the present invention relates to non-aqueous electrochemical cells, comprising: (i) anode; (ii) mixed cathode; It comprises that the first fluorocarbons cathode material, the second fluorocarbons cathode material and the 3rd fluoridize carbon cathode material; Wherein, (a) said first, second with the 3rd fluoridize carbon cathode material every kind present the discharge voltage that is different from other about 2.5V of two kinds or is higher than about 2.5V, and (b) when discharging into about 1.5V, the discharge capacity of the said first fluorocarbons cathode material is the about 870mAh/g of about 800mAh/g-; The discharge capacity of the said second fluorocarbons cathode material is the about 800mAh/g of about 680mAh/g-, and the said the 3rd fluoridize carbon cathode material discharge capacity be the about 875mAh/g of about 825mAh/g-; (iii) be arranged on the dividing plate between said anode and the said negative electrode; And the nonaqueous electrolytic solution that (iv) is communicated with said anode, said negative electrode and said dividing plate fluid.Randomly, the said first and second fluorocarbons cathode materials derive from petroleum coke, and/or the said the 3rd fluoridizes carbon cathode material and derive from petroleum asphalt.
The present invention also further relates to the various electronic equipments that comprise such non-aqueous electrochemical cells.
Should be noted that without departing from the scope of the invention, one or more supplementary features that can will be discussed in more detail below are incorporated in one or more above-mentioned embodiments.
Brief description of drawings
Fig. 1 is the photo of bead active carbon before fluorination that derives from petroleum asphalt.
Fig. 2 is the microphoto as the fluorocarbons particle of cathode material.
Fig. 3 is the fluorocarbons (CF that derives from petroleum coke 1) and bead derive from the diagram of X-ray diffractogram of the fluorocarbons of petroleum asphalt.
Fig. 4 is the fluorocarbons (CF that derives from petroleum coke 1) the diagram of x-ray photoelectron power spectrum (F1) of particle surface.
Fig. 5 is the fluorocarbons (CF that derives from petroleum coke 1) the diagram of x-ray photoelectron power spectrum (C1) of particle surface.
Fig. 6 derives from the diagram of x-ray photoelectron power spectrum (F1) of particle surface of the fluorocarbons of petroleum asphalt for bead.
Fig. 7 derives from the diagram of x-ray photoelectron power spectrum (C1) of particle surface of the fluorocarbons of petroleum asphalt for bead.
Fig. 8 is the fluorocarbons (CF that derives from petroleum coke 1) at room temperature utilize the diagram of discharge curve of the discharge rate of 20mA/g.
Fig. 9 is the fluorocarbons (CF that derives from petroleum coke 0.6) at room temperature utilize the diagram of discharge curve of the discharge rate of 20mA/g.
The fluorocarbons that Figure 10 derives from petroleum asphalt for bead at room temperature utilizes the diagram of discharge curve of the discharge rate of 20mA/g.
Figure 11 at room temperature utilizes the diagram of discharge curve of the discharge rate of 20mA/g for the mixed cathode of one embodiment of the invention, said mixed cathode contains the fluorocarbons of the data that are useful on generation Fig. 8-10.
Figure 12 is the diagram of discharge curve of Li/CF electrochemical cell and the Li/CF non-aqueous electrochemical cells of the present invention of prior art, and Li/CF non-aqueous electrochemical cells of the present invention contains the mixed cathode of embodiment of the present invention of using the 50J pulse.
Figure 13 contains the diagram that bead derives from fluorocarbons with the discharge curve of the electrochemical cell of the mixed cathode of embodiment of the present invention of using the 50J pulse of petroleum asphalt.
Figure 14 contains the diagram that bead derives from fluorocarbons with the discharge curve of the electrochemical cell of the mixed cathode of embodiment of the present invention of using the 80J pulse of petroleum asphalt.
Figure 15 be contain bead derive from petroleum asphalt fluorocarbons electrochemical cell with contain the fluorocarbons (CF that derives from petroleum coke 1) the diagram of the heat that in discharge process, produces of battery.
Invention specifically describes
The present invention relates to contain multiple different cathode material, and more specifically contain the mixed cathode of three kinds of visibly different fluorocarbonss (CF) cathode material.The difference of said each fluorocarbons cathode material is that every kind demonstrates different discharge curves (promptly; At about 2.5V or be higher than the different discharge voltage of about 2.5V; And when discharging into about 1.5V different discharge capacity); And/or difference is that one or more said fluorocarbons cathode materials derive from different carbon (for example, petroleum coke or petroleum asphalt).More particularly; In one embodiment; The characteristic of said three kinds of different fluorocarbons cathode materials can be; (a) the said first or the 3rd fluoridize carbon cathode material average degree of fluorination be different from the said second fluorocarbons cathode material and (b) the said first fluorocarbons cathode material and the randomly said second fluorocarbons cathode material derive from petroleum coke, and the said the 3rd fluoridizes carbon cathode material and derives from petroleum asphalt.In addition, the said first and the 3rd fluoridize carbon cathode material average degree of fluorination can be roughly the same.
In the embodiment of this or replacement; The characteristic of said three kinds of different fluorocarbons cathode materials can be (a) said first, second with the 3rd fluoridize every kind of demonstration of carbon cathode material be different from other two at about 2.5V or be higher than the discharge voltage of about 2.5V; And (b) when discharging into about 1.5 V; The discharge capacity of the said first fluorocarbons cathode material is the about 870mAh/g of about 800mAh/g-; The discharge capacity of the said second fluorocarbons cathode material is the about 800mAh/g of about 680mAh/g-, and the said the 3rd fluoridize carbon cathode material discharge capacity be the about 875mAh/g of about 825mAh/g-.
The invention still further relates to the non-aqueous electrochemical cells that comprises such cathode material, especially is the battery of lithium base (that is the non-aqueous electrochemical cells of lithium or lithium ion).Every kind of performance characteristics that advantageously helps and be used to improve or improve said non-aqueous electrochemical cells of three kinds of different cathode materials of the present invention (it is the part of said non-aqueous electrochemical cells).For example; In a concrete embodiment; Said three kinds of cathode materials (it is the part of said non-aqueous electrochemical cells) play improvement or improve the overall operation voltage of said non-aqueous electrochemical cells and/or the effect of energy density; Make it possible to realize high working voltage (voltage that for example, is higher than about 2.5V) and/or high-energy-density.
In this regard, should be noted that like what use among the application, " non-water " is meant the electrochemical cell that comprises or utilize the electrolyte of the water that does not contain interpolation; That is, that water does not separate as it or divide other component to join in the electrolyte, yet can be used as the organic solvent (class) that is used to prepare said electrolyte trace or solvent or pollutant exist.For example; In one or more indefiniteness embodiments of the present invention, the water content of said electrolyte usually can be less than about 1000ppm, less than about 750ppm, less than about 500ppm, less than about 250ppm, less than about 100ppm, less than about 50ppm, less than about 25ppm or even littler.
In this regard, be to be further noted that and think that in this application " electrochemical cell " is battery pack, capacitor, battery, electrochemical apparatus etc.Should be appreciated that these reference substances do not limit, and any battery that relates to electron transfer between electrode and the electrolyte is deemed to be within the scope of the present invention all.
In this regard; Also should further notice; " improvement " or " raising " performance characteristics generally is meant: for example compare with the non-aqueous electrochemical cells of similar preparation or design but two kinds of not containing just like describe in detail among the application or more kinds of different fluorocarbons cathode material, non-aqueous electrochemical cells of the present invention specific energy, energy density, operating voltage and/or high rate performance ( Rate capability) improvement or the raising of aspect.
1. cathode material composition and battery components
According to the present invention; And below in greater detail like the application; The applicant has been found that one or more performance characteristicses of non-aqueous electrochemical cells can improve or improve through the negative electrode (that is, use " mixed cathode ") that use contains three kinds of different fluorinated carbon materials.In this regard, should be noted that the applicant has been found that the combination of said three kinds of different fluorinated carbon materials makes non-aqueous electrochemical cells have high working voltage and high-energy-density.
According to the present invention, the said first fluorocarbons cathode material can be expressed as formula CF basically x, wherein the mean value of x is from greater than about 0.9 to about 1.2, or from about 0.95 to about 1.15, and in a concrete embodiment, be about 1.The said second fluorocarbons cathode material can be expressed as formula CF basically y, wherein the mean value of y is from about 0.4 to less than about 0.9, or from about 0.5 to about 0.7, and in a concrete embodiment, be about 0.6.The said the 3rd fluoridizes carbon cathode material can be expressed as formula CF basically z, wherein the mean value of z is about 1.2 for about 0.8-, or about 0.9-is about 1.1, and in a concrete embodiment, is about 1.In this regard, should be noted that in one or more concrete embodiments, the mean value of each of x, y and z is being different within other above-mentioned scope of two.Yet in the embodiment of one or more replacements, the mean value of x and z can be within roughly the same above-mentioned scope, but is different from the scope of y.
In this regard; Be to be further noted that as carrying out best explain more below, in each embodiment; First, second of said fluorocarbons cathode material and/or the 3rd component can derive from identical carbon source (for example, petroleum coke or pitch) or different sources.Yet in a concrete embodiment, said first fluorocarbons cathode material and the randomly said second fluorocarbons cathode material derive from petroleum coke, and the said the 3rd fluoridizes carbon cathode material and derive from petroleum asphalt.
Formula CF x(wherein; The mean value of x is from greater than about 0.9 to about 1.2) the total amount of fluorocarbons cathode material can be the about 70 weight % of about 20 weight %-; And more generally can be the about 65 weight % of about 25 weight %-; Or the about 60 weight % of about 30 weight %-(wherein, " weight % " is meant the value of the weight of the said first fluorocarbons cathode material with respect to the total weight that is present in the fluorinated carbon material in the said negative electrode, and randomly; When except fluorocarbons, not having material to be present in the said negative electrode, in the total weight of active cathode material).Additionally or alternatively, formula CF yThe amount of the fluorocarbons cathode material of (wherein, the mean value of y is to less than about 0.9 from about 0.4) can be the about 35 weight % of about 2 weight %-, and more generally can be the about 30 weight % of about 4 weight %-, or the about 25 weight % of about 5 weight %-.Additionally or alternatively, formula CF zThe amount of the fluorocarbons cathode material of (wherein, the mean value of z is about 0.8-about 1.2) can be the about 90 weight % of about 10 weight %-, and more generally can be the about 85 weight % of about 15 weight %-, or the about 80 weight % of about 20 weight %-.Yet, in this regard, should be understood that every kind the concentration that is present in these fluorinated carbon materials in the said negative electrode can be according to the application or the purposes that provide, mainly be optimized through mode well known in the art; Therefore, without departing from the scope of the invention, above-mentioned first, second and the 3rd fluoridized the concentration of material with carbon element can be with except that existing like the amount describing among the application.
Fluorinated carbon material of the present invention can mainly utilize method known to a person of ordinary skill in the art or technology preparation.For example, such material mainly can pass through carbon source and fluoro-gas contact preparation.Yet, have been found that said carbon source can influence the discharge performance of said non-aqueous electrochemical cells, even have identical or similarly also like this during degree of fluorination when said material.For example, carbon is about 1:1 with the mol ratio of fluorine, the fluorocarbons (Fig. 8) that derives from petroleum coke has different discharge curves with the fluorocarbons (Figure 10) that has similar mol ratio but derive from bead petroleum asphalt.According to embodiment of the present invention; Said material with carbon element can derive from petroleum coke, bead petroleum asphalt (it can be or can not be activation) (Fig. 1 and 2), other active carbon (for example; Charcoal (charcoal)); And graphite material, like natural with synthetic graphite and all its derivatives that comprise Graphene, graphite nano plate, expanded graphite (expanded graphite), carbon nano-fiber and CNT.Have been found that petroleum coke especially is suitable as cathode material.Bead petroleum asphalt also is fit to use with granularity narrow distribution, flowability, high-purity and high strength and resistance to wear owing to it is little.
Negative electrode of the present invention can contain in carbon source (said cathode material derives from this carbon source) goes up two kinds different or more kinds of fluorocarbons cathode materials.In exemplary embodiment, said negative electrode had both contained the fluorinated carbon material that the fluorinated carbon material that derives from petroleum coke also contains the petroleum asphalt that derives from bead and activity.In this regard; To be present in the total weight of the fluorinated carbon material in the said negative electrode; The total amount of the said fluorocarbons cathode material that derives from petroleum coke can for about 20%-about 80% (for example; At least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, and less than about 30%, less than about 40%, less than about 50%, less than about 60% or less than about 70%).In addition; To be present in the total weight of the fluorinated carbon material in the said negative electrode; Derive from bead petroleum asphalt the fluorocarbons cathode material amount can for about 30%-about 80% (for example; At least about 40%, at least about 50%, at least about 60%, at least about 70%, and less than about 40%, less than about 50%, less than about 60% or less than about 70%).
In each embodiment, derive from petroleum coke fluorocarbons average BET surface area can for, for example, about 120cm 2The about 450cm of/g- 2/ g, or about 180cm 2The about 250cm of/g- 2/ g.The fluorocarbons that derives from petroleum asphalt has higher a little BET surface area usually, for example, and about 250cm 2The about 750cm of/g- 2/ g, or about 350cm 2The about 650cm of/g- 2/ g.Yet, in this regard, should be noted that; No matter it derives from any source; Without departing from the scope of the invention, the surface area of said fluorocarbons cathode material can be fallen within any scope of narrating, or replacedly can drop on outside any scope of narrating.
The first above-mentioned fluorocarbons cathode material (for example, derives from the for example CF in coke source 1) can be for example, as PC-10 CF from Lodestar (New Jersey) 1Be purchased.The second above-mentioned fluorocarbons cathode material (for example, also derives from the for example CF in coke source 0.6) can for example be purchased as the PC-51 from Lodestar.The above-mentioned the 3rd fluoridizes carbon cathode material (for example, derives from the for example CF of pitch 0.9-1.1) can be for example, as (Tulsa, P5000 Oklahoma) is purchased from Advanced Research Chemical.Yet, in this regard, should be noted that, without departing from the scope of the invention, can use other material.
Should be understood that; Said negative electrode can contain one or more other cathode material; As at for example U.S. Patent application No.12/614; The copper manganese mixed oxides of describing in 667 (the announcing (being filed on November 9th, 2009) as the open text No. 2010/0221616 of the U.S.), from all relevant and consistent purpose, said application is incorporated among the application by reference.For example, in each embodiment, said negative electrode can comprise a certain amount of by formula Cu aMn bO cOr Cu aMn bO cNH 2O (" nH wherein 2O " expression be present in the said cathode material constitution water and/or the surface water) expression the copper manganese oxide cathode material.In this cathode material, the oxidation state of copper can be approximately+1 to approximately+3, and the oxidation state of manganese can be approximately+2 to approximately+7.In addition; The value of each of a, b and c is independently greater than 0; And (i) the a+b sum can be about 3 for about 1-, and (ii) the value of c can be confirmed experimentally, and its value with the oxidation state of a, b and copper and manganese is consistent; And in one or more embodiments, the value of c makes the oxidation state of copper be about+2 or higher.Said copper Mn oxide material can be in form amorphous or replacedly for hemicrystalline.
In this regard; Should be noted that; In a specific embodiment, said first, second with the 3rd fluoridize material with carbon element summation account for about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% or even about 100% (based on total weight that is present in cathode material wherein) of the cathode material in the negative electrode that is present in said non-aqueous electrochemical cells.In the embodiment of each replacement; The concentration of wherein said fluorinated carbon material is less than about 100%; Can be according to the application that provides or purposes, through mode well known in the art the concentration that is present in one or more the additional cathode materials (for example, copper Mn oxide) in the said negative electrode is optimized.In a concrete embodiment; Yet; Cathode mix of the present invention can comprise the fluorocarbons of the about 95 weight % of about 60 weight %-, and in some cases, can comprise the fluorocarbons of the about 90 weight % of about 65 weight %-; Or the fluorocarbons (that is the total concentration of said three kinds of different fluorinated carbon materials) of the about 85 weight % of about 70 weight %-.In addition, said cathode mix can comprise the copper Mn oxide of the about 40 weight % of about 5 weight %-, and can comprise the copper Mn oxide of the about 35 weight % of about 10 weight %-in some cases, or the copper Mn oxide of the about 30 weight % of about 15 weight %-.Yet, in this regard, should be noted that the form that should such concentration is not regarded as limiting.For example, in the embodiment of replacement, said copper Mn oxide can be the key component of said cathode material (rather than for example said fluorocarbons).
The fluorinated carbon material of in the application, describing, other component of said non-aqueous electrochemical cells can be selected from well known in the art those.For example; According to each embodiment of the present invention; Said negative electrode can also comprise adhesive; For example, natural or synthetic polymer adhesive is like the copolymer of Kynoar (PVDF), polytetrafluoroethylene (PTFE), ultra-high molecular weight polyethylene (UHMWPE), butadiene-styrene rubber, cellulose, lactoprene and acrylic acid or acrylic acid ester.Said negative electrode can contain (in the weight of active material of cathode, adhesive and conductive filler (will be described below)) and reach about 15% adhesive (for example, about 1%-about 15%) and more generally reach about 9% adhesive (for example, about 1%-about 9%).
Except said adhesive, can said fluorinated carbon material be mixed with the additive or the filler of conduction.Suitable additive comprises that carbon black (for example; Super P from Timcal), natural and synthetic graphite, with and the carbon of various derivative (comprise Graphene, graphite nano plate, expanded graphite-like KS4), carbon nano-fiber and nanotube and non-graphite form from Timcal, like coke, charcoal or active carbon.Various metals (especially powder type those) also can be as the conductive filler in the said negative electrode, and in some embodiments, and will be under the current potential that is higher than 3.0 V not oxidized metal uses with (versus) lithium simultaneously.The instance of such metal comprises silver, gold, aluminium, titanium and composition thereof.
Said negative electrode can contain (in the weight of active material of cathode, adhesive and conductive filler) and reach about 15 weight % conductive additives (for example, the about 15 weight % of about 1 weight %-).More generally, however said negative electrode can contain the conductive additive (for example, the about 10 weight % of about 1 weight %-) that reaches about 10 weight %.In this regard, should be noted that lower resistivity or high conductivity mean at said fluorocarbons (CF) because discharge becomes before the conduction, said negative electrode can the starting point in life-span ( Beginning-of-life) higher-wattage is provided.
In some embodiments, said negative electrode comprises the polymeric material as adhesive and conductive filler.Such material can be conjugated polymer (that is, the n-of conjugation unit polymerization-filling thing), like polypyrrole, polythiophene, polyaniline and composition thereof.In such embodiment, usually said conducting polymer is mixed with said fluorocarbons (CF) active material or it is put on wherein, in order to minimum possible cathode resistor rate to be provided.
Be to be further noted that each embodiment of the present invention comprises that cathode material wherein is the embodiment of non-lithiumation.In other words, said cathode material is feasible through preparing, at least (promptly at first; Before the use); Lithium in the said cathode material or lithium ion on basically be dissociate (that is, and in the preparation process, be not meant to lithium or the lithium ion component as said cathode material is added).In a concrete embodiment, said negative electrode basically by fluorocarbons and randomly adhesive material and/or the conduction diluent (all describing in further detail) like other part among the application form.Yet, can such cathode material be used for have the non-aqueous electrochemical cells of lithium (Li) anode, be used for once the battery of (not rechargeable) or secondary (rechargeable).Therefore, lithium or lithium ion may reside in such cathode material.In use, the existence of such lithium or the lithium ion form that should not be regarded as limiting.
In addition, non-aqueous electrochemical cells of the present invention has anode, and this anode can comprise any anode material that is suitable in the non-aqueous electrochemical cells.Yet normally, said anode comprises metal; This metal is selected from the IA family or the IIA family of the periodic table of elements; For example comprise, lithium, magnesium, sodium, potassium etc., with and alloy and intermetallic compound; For example comprise Li-Mg, Li-Al, Li-Al-Mg, Li-Si, Li-B and Li-Si-B alloy and intermetallic compound.The form of said anode can change, but usually with its be made as the anode metal thin foil with have the elongation formula lug plate that is fixed in said anode foils ( Extended tab) or the lead-in wire current-collector.Said anode capacity can be for waiting until the capacity big about 35% than said negative electrode from about with said cathode capacities mutually.
As previously mentioned, non-aqueous electrochemical cells of the present invention also comprises electrolyte non-water, ionic conduction, and in the electrochemical reaction process of said battery, this electrolyte moves the path of usefulness between said anode and said cathode electrode as ion.It is liquid or solid-state that said electrolyte can be, perhaps both.Electrochemical reaction on the said electrode comprises the ion conversion of moving to the atom or the molecular forms of said negative electrode from said anode.Therefore, being suitable for nonaqueous electrolytic solution of the present invention is chemically inert for said anode and cathode material basically.And suitable liquid electrolyte is shown as those physical propertys (for example, low viscosity, low surface tension and/or good wetability) that help ion and carry.
The various components of said electrolyte can be selected from well known in the art those, it is fit to be used in combination with cathode material of other part detailed description of the application.Yet, preferably, be used for suitable electrolytes according to the present invention and have the salt inorganic, ionic conduction in the nonaqueous solvents of being dissolved in (maybe when using solvent mixture, being dicyandiamide solution).More preferably, said electrolyte comprises the ionizable alkali metal salt that is dissolved in sprotic organic solvent or the solvent mixture (it comprises low adhesive solvent and high dielectric constant solvent).Do not rely on any concrete theory, believe said salt inorganic, ionic conduction as the migration of said anode ion with the carrier of said active material of cathode reaction.Therefore, the alkali metal salt of said formation ion can be similar to the alkali metal that comprises said anode.
In a concrete embodiment of the present invention, the general formula of the salt of said ionic conduction is MM ' F 6Or MM ' F 4, wherein M be with said anode in the identical alkali metal of at least a metal, and M ' is for being selected from the element of three valent phosphors, arsenic, antimony and boron.Be suitable for obtaining formula M ' F 6Salt comprise, for example, hexafluorophosphate (PF 6), hexafluoro arsenate (AsF 6) and hexafluoro antimonate (SbF 6), and be suitable for obtaining formula M ' F 4Salt comprise, for example, tetrafluoroborate (BF 4).Replacedly, can use corresponding sodium salts or sylvite.Therefore, for lithium anode, the alkali metal salt of said electrolyte can randomly be selected from, for example, and LiPF 6, LiAsF 6, LiSbF 6And LiBF 4And composition thereof.The salt of other that can use with lithium anode comprises, for example, and LiClO 4, LiAlCl 4, LiGaCl 4, LiC (SO 2CF 3) 3, LiB (C 6H 4O 2) 2, LiN (SO 2CF 3) 2, LiN (SO 2C 2F 5) 2, LiB (C 2O 4) 2, Li (CF 3SO 3) and composition thereof.
Go for the low adhesive solvent in said non-aqueous electrochemical cells of the present invention and comprise, for example, various lactone, ester class, carbonates, sulfonic acid esters, sulfurous esters, nitrile and ethers.More particularly; Yet; Said solvent can be selected from; For example; Dimethyl carbonate (DMC), diethyl carbonate, 1,2-dimethoxy-ethane (DME), oxolane (THF), methyl acetate (MA), diethylene glycol dimethyl ether, triglyme, tetraethylene glycol dimethyl ether, methyl ethyl carbonate, vinylene carbonate, dioxolanes, dioxane, dimethoxy-ethane and high dielectric constant solvent, it comprises; For example, cyclic carbonates, cyclic ester class and cyclic amide (like propylene carbonate (PC), carbonic acid ethylidene ester (EC), acetonitrile, methyl-sulfoxide, dimethyl formamide, dimethylacetylamide, gamma-butyrolacton (GBL) and N-methyl-pyrrolidones (NMP)) and various mixture or combination.
The solvent types and the composition of said electrolyte be can select to be used for, and/or the kind of salt wherein and one or more physical characteristics and/or the performance characteristics that concentration is optimized non-aqueous electrochemical cells of the present invention are present in.For example, in one or more embodiments of the present invention, the concentration of the salt in the said electrolyte can be about 2.5 M of about 0.3 M-, or about 2 M of about 0.4 M-, or about 1.6 M of about 0.5 M-.In these or other embodiment of the present invention; Wherein used mixed solvent system, first solvent (for example, carbonate solvent; Like propylene carbonate) and second solvent is (for example; Substituted alkane solvents, as 1,2-dimethoxy-ethane) (volume) ratio is as being the about 9:1 of about 1:9-; That is, said dicyandiamide solution can comprise first solvent of the about 90 volume % of about 10 volume %-or about 80 volume % of about 20 volume %-or the about 70 volume % of about 30 volume %-, and all or nearly all surplus of said solvent is said second solvent.Yet in one embodiment, said anode is the lithium metal, and preferred electrolyte is the LiBF in the PC/DME mixed solvent system of about 1.8 M of about 1 M-or about 1.6 M of about 1.2 M- 4(concentration of said dicyandiamide solution is about 10 volume %PC/90 volume % DME and about 70 volume % PC/30 volume % DME).The weight % that is included in the electrolyte in the said battery can be the about 120 weight % of about 40 weight %-of the amount that joins the active material of cathode (for example, fluorinated carbon material) in the said battery, or even the about 100 weight % of about 50 weight %-.
In addition, non-aqueous electrochemical cells of the present invention comprises suitable separator material, and this dividing plate is through selecting with the anode/anode material isolation with said negative electrode/cathode material and IA family or IIA family, thereby prevents the internal short-circuit situation.Said dividing plate be selected from usually electric insulation (and sometimes ionic conduction) not with the material known in the art of said anode and active material of cathode generation chemical reaction, and said anode and active material of cathode be not with said electrolyte generation chemical reaction and be insoluble in wherein.In addition, said separator material is through selecting to make the porosity that has be enough to make in the electrochemical reaction process at said battery said electrolyte to flow through it.Can be with said battery manufacturing so that said dividing plate is reeled between said anode and said negative electrode or heat-sealing around one or two of said anode and said negative electrode.Can select thickness for example to be the about 75 μ m of about 15 μ m-, or the separator material of the about 50 μ m of about 10 μ m-.In some embodiments, said dividing plate is that its gross thickness is the two-layer of top recited amounts scope or the laminate of multilayer more.
Therefore, suitable separator material generally includes, and maybe can be selected from polymer film porous or atresia; As for example; Polypropylene, polyethylene, polyamide (for example, polyamide fibre), polysulfones, Vingon (PVC) and materials similar and combination (for example, trilamellar membrane thereof; Like polypropylene, polyethylene/polyacrylic trilamellar membrane) and from the woven fabric of fluorinated polymers fibres; It comprises, for example, Kynoar (PVDF), Kynoar-hexafluoropropylene (cohydrofluorpropylene) (PVDF-HFP), tetrafluoroethylene-ethylene copolymer (PETFE), chlorotrifluoroethylene-ethylene copolymer and combination thereof.Can use separately or its layer is combined into microporous barrier (for example, fluorinated polymer microporous barrier) from the woven fabric of these fluorinated polymers fibres.
The form of non-aqueous electrochemical cells of the present invention or the structure can be selected from basically known in the art those.Said battery can be multiple the configuration structure, said multiple configuration comprises, for example, the volume core ( Jelly-roll), the folding anode of Z-and parallel-plate negative electrode or parallel many plates (being used for anode and negative electrode) configuration.Said negative electrode can cover with on the said anode, is interting one deck or two-layer dividing plate therebetween.Said anode capacity is generally from approximating said cathode capacities greatly to bigger by about 15%, about 25% or even about 35% than said cathode capacities.
Yet in a concrete embodiment; The form of said non-aqueous electrochemical cells or be configured to the design of valve jacket-negativity; Wherein said cathode/anode/dividing plate/electrolyte assembly is enclosed in the conducting metal valve jacket so that said valve jacket be connected in valve jacket-negative structure ( Case-negative configuration) in anode collector, although the design of valve jacket-neutrality also is suitable.The preferable material that is used for said valve jacket comprises titanium, stainless steel, nickel and aluminium.Said valve jacket head comprises crown cap, this crown cap have the perforate of working majority purpose with hold glass to the seal/terminal contact pin (terminal contact pin) of metal (said cathode electrode through said perforate charging ( Feed through for the cathode electrode)).Said anode electrode preferably is connected in said valve jacket.For the electrolyte filling provides extra perforate.Said valve jacket head comprises that other assembly with said non-aqueous electrochemical cells has compatible and can corrosion resistant parts.Then; Said battery is filled with electrolyte solution above-mentioned among the application; It is about 120% that the weight of said electrolyte is generally about 40%-of said fluorocarbons weight, or about 60%-is about 110%, and then as through soldering stainless steel plug above said filler opening it being sealed.Yet, in this regard, should be noted that, replacedly, can battery of the present invention be constructed with the design of valve jacket-positivity.The form that therefore, should the description that provide among the application is not regarded as limiting.The shape of said valve jacket is inessential, and can be button, columniform or rectangle or other shape.
In this regard, be to be further noted that without departing from the scope of the invention, other assembly of said non-aqueous electrochemical cells (for example, current-collector etc.) can be selected from those assemblies well known in the art.Said current-collector can be by aluminium, titanium, stainless steel or carbon steel structure, and can with its be configured to paper tinsel, chemical erosion sieve plate, metal lath ( Expanded metal), the perforation sieve plate ( Punched screen) or porous foil.Can utilize carbon, rare metal or carbide type coating to apply said current-collector.The active fluorinated carbon material of this coating utilization provides stable resistance at the electrochemical interface place of said current-collector.Also can the fluorocarbons of said drying be extruded or be coated on the unbonded base material forming self-supporting plate (subsequently this self-supporting plate being struck out certain size (punched to size)), and it is applied on this current-collector through compacting.Replacedly, said cathode mix can be slurry or paste form, and it is put on paper tinsel or the porous foil, is dried then.No matter what the preparation method is, can or roll to minimum thickness and the power capacity of the said battery of not negative effect the compression of said negative electrode.The total amount that is applied to the cathode material on the said current-collector can be about 7mg/cm 2-Yue 150mg/cm 2Or about 7mg/cm 2-Yue 80mg/cm 2
In case (for example pass through with said activated cathode component; Fluorocarbons), adhesive and conductive additive mix and prepare said cathode material; Just can with this cathode material with list, uniformly form of mixtures deposits on the said cathode collector and (for example, wherein with each said single fluorocarbons cathode material blend, promptly mixes basically; Make said material fully evenly distribute each other, then this mixture is deposited on the said cathode collector with form of single sheet).Yet replacedly, can each said single fluorinated carbon material be deposited on layer form: (i) (for example, (its formula is CF with the fluorocarbons that derives from coke in the same side of said current-collector x, x is for from greater than about 0.9 to about 1.2) deposit on the surface of said current-collector as ground floor, (its formula is CF will to derive from the fluorocarbons of petroleum asphalt then z, z is about 0.8-about 1.2) deposit on the said ground floor as the second layer, and (its formula is CF will to derive from the fluorocarbons of coke y, y for from about 0.4 to less than about 0.9) be deposited on the said second layer as the 3rd, or any above-mentioned combination); Or (ii) said current-collector relatively ( Opposite) side (for example, as in three-fies system, wherein be deposited upon a side with two and be deposited upon opposite side, or be deposited on the opposite side of said current-collector in a side and with the third material as monolayer deposition with two kinds of component blend and with the material of this blend).These with various other embodiments in, be generally the about 35mg/cm of about 5-in the carrying capacity of the lip-deep cathode material of said current-collector 2(every side), or the about 30mg/cm of about 6- 2, and suitably can be the about 21mg/cm of about 7- 2
In an exemplary embodiment, prepare said negative electrode (this mixture is the polymer adhesive of fluorocarbons active material, the conduction diluent that reaches about 15 weight % and the about 9 weight % of about 2-of the about 94 weight % of about 82-) through the dried mixture on the contact current-collector.Sieve plate, metal lath, perforation sieve plate or the porous foil form of paper tinsel, chemical erosion processed and be to said current-collector by aluminium, titanium, stainless steel or carbon.Said current-collector preferably applies with carbon, rare metal or carbide type coating.Utilize said fluorocarbons (CF) stable resistance to be provided at the electrochemical interface place of said current-collector.Also can the CF mixture of said drying be extruded or be coated on the unbonded base material forming self-supporting plate (subsequently this self-supporting plate being struck out certain size), and it is applied on this current-collector through compacting.Replacedly, can the cathode mix of the slurry or the form of paste be put on paper tinsel or the porous foil, then that said negative electrode is dry.No matter what the preparation method is, all with the compression of said negative electrode or roll to minimum thickness and the power-performance of the said battery of not negative effect.The amount of said cathode material is generally about 7mg/cm 2-Yue 150mg/cm 2
It should be noted that unless otherwise indicated, otherwise the various concentration of narrating among the application, concentration range, degree, ratio etc. are only as purpose of explanation and usefulness, therefore should be with its form that is regarded as limiting.The whole various combinations that it should be noted that composition, concentration, degree, ratio, component etc. in addition all are intended within scope of the present invention and supported by it with arranging.
2. cathode material preparation
Known method prepares said fluorinated carbon material by one of skill in the art; As through in reaction vessel with said carbon source (for example; Coke (like petroleum coke), active bead petroleum asphalt, active carbon (BAC), active carbon, charcoal and the graphite material of bead) and fluoro-gas is (for example; Be diluted in the fluorine gas in the inert carrier gas, this inert carrier gas such as nitrogen or argon gas or its mixture) Continuous Contact.Can make the fluoro-gas of consumption from said reaction vessel, continue to discharge.Normally, said fluorination reaction can take place under the temperature of about room temperature-Yue 550 ℃, but under about 300 ℃-Yue 450 ℃ temperature, takes place usually.In addition, this reaction can be at atmospheric pressure or is replacedly taken place down at high pressure (that is, being higher than atmospheric pressure).Said carbon granule is contacted with fluoro-gas up to obtaining desirable degree of fluorination (as confirming through means known in the art); Yet; (for example depend on the reaction system variable; Said reactive component, fluoro-gas concentration and flow velocity, required degree of fluorination, operating temperature, pressure etc.), the suitable reaction time can for example be about 30 hours of about 1 hour-Yue 40 hours or about 35 hours of about 4-or about 6-.Although use the amount and/or the concentration in the gas of fluorine to change in the technology, it should be noted that the amount of preferably controlling said fluorine is to limit excessive fluorine, because excessive fluorine possibly cause the formation of gaseous products and the damage of corresponding solid carbon.
Referring now to Fig. 1, in a concrete embodiment, the active carbon (BAC) of bead is used to prepare said fluorocarbons cathode material.BAC is as the spherical active carbon of the height of its raw material with petroleum asphalt.Except the absorbent properties that active carbon has inherently; BAC also has various characteristics, for example comprises: small grain size, high fill volume, high fluidity, high-purity, low dustiness (low dust content), high strength, high-wearing feature and narrow particle size distribution.In addition, BAC relies on the integration production and supply from material asphalt to go out the stable high quality product.And, BAC have derive from use high-grade pitch, do not use adhesive to form bead and evenly flood when mobile ( Infusibilization) and the good characteristic of activation.Common BAC prepares process and comprises the steps:
Figure 262570DEST_PATH_IMAGE001
As stated, can said material with carbon element be fluoridized up to the required average degree of fluorination (that is, the x in above-mentioned formula, y and/or z reach desirable mean value) that obtains for the fluorocarbons of three kinds of variety classeses or form.In general, yet, can carry out fluorination up to obtaining suitable fluorinated carbon material.Normally, the characteristic of such material can be that the mol ratio of carbon and fluorine is the about 1:1.9 of about 1:0.1-, or the about 1:1.2 of about 1:0.4-characterizes; In other words, normally, the characteristic of suitable fluorocarbons can be formula CF q, wherein q is about 1.9 for about 0.1-, or about 1.2 (therefore, the formula CF of about 0.4- qComprise substantially by formula CF x, CF yAnd CF zThree kinds of fluorinated carbon materials of expression).
The granularity that is used for the fluorocarbons of said negative electrode can change without departing from the scope of the invention.For example, derive from fluorocarbons (for example, the CF of petroleum asphalt (for example, bead petroleum asphalt) z) particle mean size (for example, nominal diameter) can be the about 1200 μ m of about 100 μ m-, or about 1000 μ m of about 150 μ m-.In some embodiment preferred, yet the average-size of such fluorocarbons is the about 700 μ m of about 500 μ m-.By contrast, derive from fluorocarbons (for example, the CF of petroleum coke x) particle mean size (for example, nominal diameter) can be the about 300 μ m of about 0.1 μ m-, and be generally the about 100 μ m of about 0.5 μ m-.
In this regard, should be noted that, can directly or through reducing granularity (using means well known in the art) obtain above-mentioned granularity.For example, in case preparation is accomplished, can randomly reduce through milling or grinding the fluorinated carbon material size that makes gained.Therefore, aptly, granularity is that the material of the about 300 μ m of about 0.1-(for example, about 0.1 μ m-Yue 200 μ m or about 0.5 μ m-Yue 50 μ m) can randomly obtain (directly or through granularity reducing) to be used for said negative electrode.
Have been found that owing to the surface area that increases the granularity in the said scope causes particulate to disperse better and higher capacity output.Liquid suspension (that is slurry) through (milling like ball milling or injection) the said particle of milling can obtain particle size aptly and reduce.Said slurry can contain the solid (for example, about 70 weight % of about 40 weight %-or the about 60 weight % of about 45 weight %-) of the about 80 weight % of 30 weight %-that have an appointment aptly.The viscosity of said slurry can be the about 2500cP of about 400cP-, and is generally the about 1600cP of about 600cP-.
3. the purposes of electrochemical cell and performance characteristics
Do not rely on any concrete theory; Should be noted that; The combination that it is believed that three kinds of (or more kinds of) different or different fluorocarbons cathode materials is especially favourable; At least part is because based on the single power and the rate capability that only contain each a kind of negative electrode in the different fluorocarbons cathode materials, and the combination of these materials makes material have unexpectedly higher than expection power and/or high rate performance.In other words; Further explain as following; Observe, be higher than the summation of the single power capacity of the similar battery that makes (said battery only comprises a kind of single fluorocarbons cathode material) like the power of the non-aqueous electrochemical cells that comprises mixed cathode (or cathode material) described in detail among the application.
Additionally or alternatively, the characteristic that is included in the single fluorocarbons in the negative electrode of the present invention can be its discharge curve, and each said discharge curve causes the whole discharge curve of said hybrid battery.In a word; Therefore; The present invention additionally or alternatively relates to non-aqueous electrochemical cells; It comprises the first fluorocarbons cathode material in appropriate section, the second fluorocarbons cathode material and the 3rd is fluoridized carbon cathode material, and said first, second fluoridized carbon cathode material and respectively appeared and be different from other discharge voltage that is in 2.5V or is higher than 2.5V of two kinds with the 3rd.
In a concrete embodiment of the present invention; The initial discharge voltage of said first fluorocarbons can be the about 2.7V of about 2.3V-; And the about 2.6V of more preferably about 2.4V-, and discharge capacity is the about 870mAh/g of about 800mAh/g-(for example referring to Fig. 8) when the said first fluorocarbons cathode material is discharged into about 1.5V.The initial discharge voltage of the said second fluorocarbons cathode material can be the about 3.1V of about 2.7V-; And the about 3.0V of more preferably about 2.8V-, and discharge capacity is the about 800mAh/g of about 680mAh/g-(for example referring to Fig. 9) when the said second fluorocarbons cathode material is discharged into about 1.5V.The characteristic of the said second fluorocarbons cathode material also can or randomly be, from about 2.9V to about 2.6V, its discharge voltage slope ( Sloping discharge voltage) be at least about 0.1V/100mAh/g, or from about 2.9V to about 2.6V, its discharge voltage slope is at least about 0.2V/100mAh/g.The said the 3rd fluoridize carbon cathode material initial discharge voltage can be the about 3.0V of about 2.6V-; And the about 2.9V of more preferably about 2.7V-, and when with the said the 3rd fluoridize carbon cathode material when discharging into about 1.5V discharge capacity be the about 875mAh/g of about 825mAh/g-(for example referring to Figure 10).The said the 3rd fluoridize carbon cathode material characteristic can or be randomly that also to about 2.6V, its discharge voltage slope is at least about 0.03V/100mAh/g from about 2.8V, or from about 2.8V to about 2.6V, its discharge voltage slope is at least about 0.05V/100mAh/g.
In this regard; Should be noted that; For one or more said fluorocarbons cathode materials, the shape of said discharge curve or said discharge curve or slope can be used as the function of discharge rate for example and change or change, and therefore should be with its form that is regarded as limiting.
Aptly, can said first, second be fluoridized carbon cathode material combination and have the power of raising and the mixed cathode of rate capability with preparation with the 3rd.Every kind of single cathode material all contributes to the discharge voltage profile (shown in figure 11) of said mixed cathode.In suitable embodiment; The initial discharge voltage of said mixed cathode can be the about 3.0V of about 2.6V-; And the about 2.9V of more preferably about 2.7V-, and when with said cathodic discharge during to about 1.5V discharge capacity be the about 875mAh/g of about 825mAh/g-(for example, referring to Figure 11).Referring to Fig. 8-11,, can find out the said fluorocarbons component that derives from pitch (or said the 3rd fluorocarbons component, CF especially referring to Figure 10 z) (its can for example for P5000) at first discharge into about 2.5V.Afterwards, the said component that derives from coke (or the said first and second fluorocarbons components, respectively be CF xAnd CF y) be the main contributor of discharge curve.At last, when reaching about 1.5V, three kinds of materials all contribute to said discharge curve.
Should be noted that the definite composition that can select said fluorocarbons cathode material is so that its terminal applies of expectation that is optimized for the performance characteristics of expectation and/or contains the non-aqueous electrochemical cells of this cathode material.Usually; Cathode material of the present invention is suitable for any basically non-aqueous electrochemical cells known in the art; Especially be designed to supply the high impulse electric current those (wherein, " height " pulse current is generally 0.5C or bigger, wherein C in amp hr rated capacity).
In this regard, be to be further noted that as using among the application, term " pulse " be meant amplitude apparently higher than the short pulse of the electric current of the prepulsing electric current before said pulse only ( Short burst)." spike train " comprises at least one current impulse.If said spike train comprises that more than a pulse it is to have open circuit short relatively conitnuous forms transmission intermittently between the said pulse so.Exemplary spike train can comprise having four 10 pulse per second (PPS)s intermittently in 15 seconds between each pulse.Usually, 10 pulse per second (PPS)s are suitable for the application of can medical treatment implanting.Yet, depending on concrete battery design and chemical characteristic, said spike train can be obviously shorter or longer.
In addition, such non-aqueous electrochemical cells that contains above-mentioned cathode material is applicable to multiple known application or equipment basically among the present invention, and it comprises, for example: Medical Devices (as pacemaker, defibrillator, cardiac monitor, delivery system, analgesic systems ( Pain management system) etc.), portable Military Electronic Equipment (Source Music, transponder, weapon are taken aim at tool etc.), offshore set-up (like sonar buoy, torpedo etc.), aerospace equipment (like deep space probe, instruction destruction system, backup power system etc.), military and commercial sensor, remote data acquisition system and other known application and equipment.Such cathode material can especially be advantageously used in medium multiplying power and/or the powerful electrochemical cell; Said battery then can be used for such equipment; (that is, use the equipment of power supply, in the situation of medium multiplying power equipment like nerve stimulator, pacemaker, implantable cardiac defibrillator and congestive heart failure equipment; It provides the electric pulse of milliampere level; And in the situation of high magnification equipment, it provides the electric pulse of ampere level, in order to control or treatment pain, muscular movement, neurological disorders, bradycardia, tachycardia and resynchronization aroused in interest ( Cardiac resynchronization) treatment).
In a concrete embodiment; Can non-aqueous electrochemical cells of the present invention be configured to reserve cell group or battery; Said thus nonaqueous electrolytic solution separates preservation with said electrode, in big temperature range, has increased the useful storage cycle of said battery pack.When needing, said nonaqueous electrolytic solution is contacted automatically with electrode, thereby said battery is moved with normal mode.
In addition, cathode material of the present invention and the non-aqueous electrochemical cells that comprises this cathode material can have one or more with other material well known in the art and battery similarly (if compare with it be not to improve or improve) other performance characteristics.For example; In each embodiment, non-aqueous electrochemical cells or the battery pack that has been found that the negative electrode that comprises the CF cathode material that contains mixing demonstrates and basically similar (if not bigger than it) power and/or the speed of other high-energy negative electrode of current use those of CF of single source (as contain).In other each embodiment; Yet; For example compare with the conventional non-aqueous electrochemical cells that uses the cathode material do not comprise three kinds or more kinds of fluorocarbons (CF) cathode material, the non-aqueous electrochemical cells that comprises cathode material of the present invention can demonstrate specific energy, energy density or capacity improvement or that improve.Additionally or alternatively; For example compare with the non-aqueous electrochemical cells like configurations that comprises conventional fluorocarbons cathode material or that make; Non-aqueous electrochemical cells of the present invention can advantageously produce less about 5%, about 10% or even about 15% heat (for example, as in the application's embodiment 5, will more specify) during use.
The present invention is specified above, clearly under not breaking away from the situation that is defined in the scope of the present invention in the appended claim, can make amendment and change.
Provide the following embodiment that does not limit in order to each detailed content of the present invention and the embodiment of further explaining.
Embodiment
Embodiment 1: the fluorocarbons (CF that derives from coke 1 ) and derive from the fluorocarbons (CF of pitch 1 ) physics and chemical characterization
Confirm to derive from fluorocarbons (that is CF, of coke x, it can be used as CF 1Be purchased, but as provide in the following table 2, its analysis is confirmed as is more approached CF 0.9) and derive from fluorocarbons (that is CF, of pitch z, like what provide in the following table 2, it is CF in this case 1) X-ray diffractogram, in order to performance and the physical structure (Fig. 3) that characterizes said CF material.There is minimum difference in the XRD signal of Fig. 3 explanation between these two kinds of CF materials.
The crystal size of said material is passed through computes:
Figure 520299DEST_PATH_IMAGE003
Wherein, L cBe crystal size, K is instrumental constant (being generally 1), and λ is the wavelength (1.54) of X ray, and L is halfwidth degree (FWHM), and θ is the angle of diffraction.Said crystal size (the L that derives from the fluorinated carbon material of coke c) be 2.99 nm, and the said carbon that derives from pitch has big slightly crystal size, is 4.5 nm.
The applicant utilizes the surface chemical property of the said material of x-ray photon energy disperse spectroscopy (XPS) research.XPS scanning survey (Fig. 4-7) has shown carbon and fluorine element on the said material surface.The more detailed scintigram and the peak thereof of carbon and fluorine are shown among Fig. 4-7.
The fluorine peak of two kinds of materials only has a main peak that occurs at the 688.3eV place.This means that fluorine all in the said material all is covalently bound on the carbon and forms the C-F key.The labor of carbon is shown in the following table 1, and the percentage of every kind of key of said material is shown in the bracket.The said material that derives from petroleum asphalt has two peaks at 288.7eV and 290.6eV place, and it represents C-F and C-F respectively 2Key.It is believed that said C-F 2Key possibly be present in the edge of said CF material.
In the situation of said fluorocarbons coke material, detailed carbon analysis is at 289eV (C-F), 290.3eV (C-F 2), 288.6eV (C 10F 8-) nAnd 287.3eV (C 4F-) nThe place has shown several peaks.Fluoridizing of reduced levels represented at two additional peaks at 288.6eV and 287.3eV place.The said fluorocarbons that derives from pitch of this data representation is mainly CF 1, and the said fluorocarbons that derives from coke has mixing with CF of little percentage 1the low fluorocarbons of fluoridizing level ( Lower fluorinated carbon).Therefore, think that the said material that derives from pitch has the better structure that is mainly made by single fluorocarbons, said single fluorocarbons can produce the initial discharge voltage that exceeds 300mV.
Table 1
Figure 977825DEST_PATH_IMAGE005
Table 1:X ray photons energy disperse spectroscopy data, its illustrated in detail the said fluorocarbons and the carbon peak and the fluorine peak that derive from the fluorocarbons of coke that derives from pitch.
Derive from the fluorocarbons (CF of pitch 1) and derive from the fluorocarbons (CF of coke 1) physical characteristic be shown in Table 2.As shown in table 2, a little higher than said material that derives from coke of fluorine concentration in the said material that derives from pitch.The granularity of the said material that derives from pitch is also than big about 40 times of the said material that derives from coke (granularity reduce before), and surface area big about 50%.Fluorocarbons cathode material that can be through deriving from pitch explain bigger surface area than small crystalline size (it causes more internal void).The said electronic scanner microscope image (Fig. 2) that derives from the material of pitch proves that the surface area of said particle is coarse, and it will produce bigger surface area.
Table 2
Figure 792198DEST_PATH_IMAGE007
Table 2: the fluorocarbons and the physical characteristic that derives from the fluorocarbons of coke that derive from pitch.
Embodiment 2: the battery of prior art is confirmed with the discharge curve (50J pulse) that contains the battery of mixed cathode of the present invention
In the aluminium bag (aluminum bag) of sealing, make up two 2.5Ah Li/CF batteries.A battery comprises the mixed cathode that contains three kinds of CF mixtures of material: the formula CF of 40 weight % 1The fluorocarbons that derives from coke, the formula CF of 10 weight % 0.6The fluorocarbons that derives from coke and the formula CF of 50 weight % 1The fluorocarbons that derives from pitch.Second Li/CF battery that battery is a prior art.Said mixed cathode also comprise as conductive filler carbon (the Super P carbon black of the KS-4 graphite of 6 weight % of said negative electrode and 4 weight % of said negative electrode, the two is all from TIMCAL) and as the Kynoar (PVDF) of adhesive.With said material mixing and be applied on the aluminum current-collector of coating with carbon.Pile up about five target dividing plates and anode and make it form said bag battery (bag cell).
Test process is made up of the 50J pulse; That is, the 50J pulse is put on two batteries (Figure 12).The spike train that puts on said battery comprises four current impulses (50J).Said pulse is to have the conitnuous forms transmission of 15 seconds open circuits weak point intermittently between the pulse.Between two continuation columns there is 4 hours open circuit intermittence.
Shown in figure 12, the battery that contains said mixed cathode has the pulse minimum voltage higher than the battery of prior art, and this maybe be owing to contain the said fluorocarbons (referring to following embodiment 3) that derives from pitch.More specifically, shown in figure 12, in the starting point in life-span, the mixed cathode that contains P5000 has the pulse minimum voltage that exceeds 500mV than the cathode material of prior art.This makes said mixed cathode under the high power discharge process, supply bigger electric energy.
Should be noted that the x axle that is described as the Figure 12-14 of " DOD " is the depth of discharge of said battery, this depth of discharge is the capacity of supply and the ratio (multiply by 100) of theoretical capacity.
Embodiment 3: the confirming of discharge curve (50J pulse) that contains the battery of the fluorocarbons negative electrode that derives from pitch
From with the purpose of embodiment 2 contrast, prepared according to the method for embodiment 2 and to have had the fluorocarbons negative electrode (CF that derives from pitch 1Or P5000) battery.Make the same 50J pulse process (Figure 13) of said battery experience and embodiment 2.Shown in figure 13, the pulse minimum voltage of life-span starting point is high for about 2.5V.Figure 13 also shows the curve of the battery of the hybrid battery that contains embodiment 2, and the minimum voltage of this battery is that 2.4 V are high.
Embodiment 4: contain the battery of mixed cathode of the present invention and confirming of the discharge curve (80J pulse) that contains the battery of the fluorocarbons negative electrode that derives from pitch
Make the battery (having the fluorocarbons component identical with the mixed cathode of embodiment 2 forms) that contains mixed cathode and have the fluorocarbons negative electrode (CF that derives from pitch 1Or P5000) battery experience is similar to the 80J discharge process (Figure 14) of embodiment 2.The pulse minimum voltage of life-span starting point that contains the battery of said mixed cathode is about 2.3V height, and it is similar to the battery (2.4V) that contains the fluorocarbons that derives from pitch.
Embodiment 5: by the comparison of the battery that contains the fluorocarbons negative electrode that derives from coke with the battery generation heat that contains the fluorocarbons negative electrode that derives from pitch
Confirmed the fluorocarbons negative electrode (CF that derives from coke by containing 1) D type battery and the D type battery with the fluorocarbons negative electrode (P5000) that derives from pitch in the steady-state discharge process at 20 ℃ of heats (Figure 15) that produce down.At milli calorimeter (millicalorimeter) (Calarus Corp., Tempe, AZ) the middle heat that produces of measuring.The said material that derives from coke of test proof lacks than the said material that derives from pitch and produces about 10% heat.
Figure 676977DEST_PATH_IMAGE008
When introducing the member of the present invention or its preferred (respectively) embodiment, word " (a) ", " a kind of (an) ", " this (the) " and " said (said) " are intended to refer to have one or more members.That term " comprises ", " comprising " and " having " is intended to refer to comprise and mean except the listed member of enumerating to have other member.
As can (for example doing various changes to above-mentioned embodiment without departing from the scope of the invention; Cathode material is formed, non-aqueous electrochemical cells component and structure etc.), the content in describing above all are included in shown in the drawings all be intended to for exemplary explaining not be to be the form that limits.

Claims (38)

1. non-aqueous electrochemical cells, it comprises:
Anode;
Mixed cathode; It comprises the first fluorocarbons cathode material, the second fluorocarbons cathode material and the 3rd is fluoridized carbon cathode material; Wherein (a) the said first or the 3rd fluoridizes carbon cathode material and has the average degree of fluorination that is different from the said second fluorocarbons cathode material; And (b) the said first fluorocarbons cathode material derives from petroleum coke, and the said the 3rd fluoridizes carbon cathode material and derive from petroleum asphalt;
Dividing plate, it is set between said anode and the said negative electrode; And
Nonaqueous electrolytic solution, it is communicated with said anode, said negative electrode and said dividing plate fluid.
2. non-aqueous electrochemical cells, it comprises:
Anode;
Mixed cathode; It comprises the first fluorocarbons cathode material, the second fluorocarbons cathode material and the 3rd is fluoridized carbon cathode material; Wherein (a) said first, second fluoridized other discharge voltage of two kinds that is different from that carbon cathode material respectively is rendered as about 2.5V or is higher than about 2.5V with the 3rd; And in (b) when discharging into about 1.5V; The discharge capacity of the said first fluorocarbons cathode material is the about 870mAh/g of about 800mAh/g-, and the discharge capacity of the said second fluorocarbons cathode material is the about 800mAh/g of about 680mAh/g-, and the said the 3rd fluoridize carbon cathode material discharge capacity be the about 875mAh/g of about 825mAh/g-;
Dividing plate, it is set between said anode and the said negative electrode; And
Nonaqueous electrolytic solution, it is communicated with said anode, said negative electrode and said dividing plate fluid.
3. non-aqueous electrochemical cells according to claim 1 and 2, wherein, the said first fluorocarbons cathode material has formula CF x, the said second fluorocarbons cathode material has formula CF y, and the said the 3rd fluoridize carbon cathode material and have formula CF z, wherein the mean value of x is about 1.2 for about 0.9-, and the mean value of y is that about 0.4-is about 0.9, and the mean value of z is about 0.8-about 1.2.
4. non-aqueous electrochemical cells according to claim 3, wherein, the mean value of said x, y and z is different.
5. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-4, wherein, the said first and second fluorocarbons cathode materials derive from the petroleum coke of fluoridizing.
6. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-5, wherein, the said the 3rd fluoridizes carbon cathode material derives from pitch.
7. non-aqueous electrochemical cells according to claim 6, wherein, said pitch is bead petroleum asphalt.
8. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-7, wherein, the said first fluorocarbons cathode material is CF 1, the said second fluorocarbons cathode material is CF 0.6, and the said the 3rd to fluoridize carbon cathode material be CF 1
9. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-8, wherein, in the total weight of fluorinated carbon material, said mixed cathode contains the first fluorocarbons cathode material of the 30%-that has an appointment about 60%.
10. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-9, wherein, in the total weight of said fluorinated carbon material, said mixed cathode contains the about 25% the second fluorocarbons cathode materials of the 5%-that has an appointment.
11. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 3-10, wherein, in the total weight of said fluorinated carbon material, said mixed cathode contains the 3rd of the 20%-that has an appointment about 80% and fluoridizes carbon cathode material.
12. non-aqueous electrochemical cells according to claim 1; Wherein, The initial discharge voltage of the said first fluorocarbons cathode material is the about 2.7V of about 2.3V-, and when the said first fluorocarbons cathode material discharged into about 1.5V, discharge capacity was the about 870mAh/g of about 800mAh/g-.
13. according to the described non-aqueous electrochemical cells of arbitrary claim in the claim 1 and 12; Wherein, The initial discharge voltage of the said second fluorocarbons cathode material is the about 3.1V of about 2.7V-; And when the said second fluorocarbons cathode material discharged into about 1.5V, discharge capacity was the about 800mAh/g of about 680mAh/g-.
14. according to the described non-aqueous electrochemical cells of arbitrary claim in the claim 1,12 and 13; Wherein, The said the 3rd fluoridize carbon cathode material initial discharge voltage be the about 3.0V of about 2.6V-; And fluoridize carbon cathode material when discharging into about 1.5V when the said the 3rd, discharge capacity is the about 875mAh/g of about 825mAh/g-.
15. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-14; Wherein, The initial discharge voltage of said mixed cathode is the about 3.0V of about 2.6V-, and when said cathodic discharge during to about 1.5V, discharge capacity is the about 875mAh/g of about 825mAh/g-.
16. non-aqueous electrochemical cells according to claim 15; Wherein, Total weight in active cathode material; Said mixed cathode contains the first fluorocarbons cathode material of the 30%-that has an appointment about 60%, the second fluorocarbons cathode material of about 5%-about 25%, and about 20%-about 80% the 3rd fluoridize carbon cathode material.
17. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-16; Wherein, Said nonaqueous electrolytic solution comprises organic solvent; This organic solvent is selected from dimethyl carbonate (DMC), diethyl carbonate, 1,2-dimethoxy-ethane (DME), oxolane (THF), methyl acetate (MA), diethylene glycol dimethyl ether, triglyme, tetraethylene glycol dimethyl ether, propylene carbonate (PC), carbonic acid ethylidene ester (EC), acetonitrile, methyl-sulfoxide, dimethyl formamide, dimethylacetylamide, gamma-butyrolacton (GBL), N-methyl-pyrrolidones (NMP), methyl ethyl carbonate, vinylene carbonate, dioxolanes, dioxane, dimethoxy-ethane or its mixture.
18. non-aqueous electrochemical cells according to claim 17, wherein, said nonaqueous electrolytic solution comprises and has formula MM ' F 6Or MM ' F 4Salt, wherein M be with said anode in the identical alkali metal of at least a metal, and M ' is for being selected from the element of three valent phosphors, arsenic, antimony and boron.
19. non-aqueous electrochemical cells according to claim 17, wherein, said nonaqueous electrolytic solution comprises and is selected from LiPF 6, LiAsF 6, LiSbF 6, LiBF 4, LiClO 4, LiAlCl 4, LiGaCl 4, LiC (SO 2CF 3) 3, LiB (C 6H 4O 2) 2, LiN (SO 2CF 3) 2, LiN (SO 2C 2F 5) 2, LiB (C 2O 4) 2, Li (SO 3CF 3) and composition thereof salt.
20. according to claim 18 or 19 described non-aqueous electrochemical cells, wherein, the concentration of the salt in the said organic solvent is about 1.6 M of about 0.5 M-.
21. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-16, wherein, said nonaqueous electrolytic solution comprises 1,2-dimethoxy-ethane, propylene carbonate and LiBF 4Salt.
22. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-21, wherein, said anode comprises the metal that is selected from periodic table of elements IA family or IIA family.
23. non-aqueous electrochemical cells according to claim 22, wherein, said anode comprises the metal that is selected from lithium, magnesium, sodium and potassium.
24. non-aqueous electrochemical cells according to claim 23, wherein, said anode comprises alloy or the intermetallic compound that is selected from Li-Mg, Li-Al, Li-Al-Mg, Li-Si, Li-B and Li-Si-B.
25. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-24; Wherein, said dividing plate comprises polypropylene, polyethylene, polyamide, polysulfones, Vingon (PVC), Kynoar (PVDF), Kynoar-hexafluoropropylene (PVDF-HFP), tetrafluoroethylene-ethylene copolymer (PETFE), chlorotrifluoroethylene-ethylene copolymer and combination thereof.
26. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-25, wherein, said negative electrode comprises conductive additive.
27. non-aqueous electrochemical cells according to claim 26, wherein, said conductive additive is selected from carbon black, natural or synthetic graphite, carbon fiber, CNT, coke, charcoal, active carbon, silver, gold, aluminium, titanium and composition thereof.
28. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-27, wherein, said negative electrode comprises adhesive.
29. non-aqueous electrochemical cells according to claim 28; Wherein, said adhesive is selected from the copolymer of Kynoar (PVDF), polytetrafluoroethylene (PTFE), ultra-high molecular weight polyethylene (UHMWPE), butadiene-styrene rubber, cellulose, lactoprene, acrylic acid or acrylic acid ester.
30. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-29, wherein, said electrochemical cell comprises the polymer as adhesive and conductive additive, this polymer is selected from polypyrrole, polythiophene, polyaniline and composition thereof.
31. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-29, wherein, the average BET surface area of the said first and second fluorocarbons cathode materials is about 120cm 2The about 450cm of/g- 2/ g.
32. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-29, wherein, the average BET surface area of the said first and second fluorocarbons cathode materials is about 180cm 2The about 250cm of/g- 2/ g.
33. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 3-32, wherein, the said the 3rd fluoridize carbon cathode material average BET surface area be about 250cm 2The about 750cm of/g- 2/ g.
34. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 3-32, wherein, the said the 3rd fluoridize carbon cathode material average BET surface area be about 350cm 2The about 560cm of/g- 2/ g.
35. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-34, wherein, the particle mean size of the said first and second fluorocarbons cathode materials is the about 800 μ m of about 0.1 μ m-.
36. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 1-34, wherein, the particle mean size of the said first and second fluorocarbons cathode materials is the about 200 μ m of about 1 μ m-.
37. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 3-36, wherein, the said the 3rd fluoridize carbon cathode material particle mean size be the about 1200 μ m of about 100 μ m-.
38. according to the described non-aqueous electrochemical cells of arbitrary claim among the claim 3-36, wherein, the said the 3rd fluoridize carbon cathode material particle mean size be the about 1000 μ m of about 150 μ m-.
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